The infra-red spectra of some organic nitrates

Carrington, Rachel

doi:10.1016/s0371-1951(60)80001-x

Cited by 26 publications

(10 citation statements)

References 3 publications

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“…Since no APN standards are currently available, the absorption cross section of the organic nitrate products at ∼ 1640 cm −1 was assumed to be identical to that from an isopropyl nitrate standard. A previous study analyzing molecular extinction coefficients of alkyl nitrates observed a standard deviation of less than 7 % among the compounds studied (Carrington, 1960), indicating that variability in the absorption cross section of organic nitrates in our study is likely not a significant source of error. Yield values were corrected for chamber wall loss and consumption by OH radicals.…”

Section: Methodsmentioning

confidence: 42%

Determination of α-pinene-derived organic nitrate yields: particle phase partitioning and hydrolysis

Rindelaub¹,

McAvey²,

Shepson³

2014

Preprint

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Abstract. The hydroxyl radical oxidation of α-pinene under high NOx conditions was studied in a photochemical reaction chamber to investigate organic nitrate (RONO2) production and partitioning between the gas and particle phases. We report an organic nitrate yield of 26 ± 7% from the oxidation of this monoterpene in the presence of nitric oxide (NO). However, the organic nitrate yield was found to be highly dependent on both chamber relative humidity (RH) and seed aerosol acidity, likely as a result of particle phase hydrolysis. The particle phase loss of organic nitrates perturbs the gas-particle equilibrium within the system, leading to decreased RONO2 yields in both the gas and particle phases at elevated RH and an apparent non-equilibrium partitioning mechanism. This resulted in smaller apparent partition coefficients of the total organic nitrate species under high chamber RH. The hydrolysis of particle phase organic nitrates at low chamber relative humidity in this study implies that aerosol partitioning of organic nitrates may be an important sink for atmospheric NOx and may have a significant impact on regional air quality.

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Section: Methodsmentioning

confidence: 42%

Determination of α-pinene-derived organic nitrate yields: particle phase partitioning and hydrolysis

Rindelaub¹,

McAvey²,

Shepson³

2014

Preprint

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“…The organic nitrate concentrations were determined using the asymmetric -ONO 2 stretch at 1640 cm −1 (Nielsen et al, 1995), using an absorption coefficient of 12 900 L mol −1 cm −1 . An uncertainty of 7 % was applied to the FTIR measurements to account for the uncertainty in the absorption coefficient when using a proxy (ethyl hexyl nitrate in this study) for -ONO 2 quantitation (Carrington, 1960). After the FTIR analysis, samples were concentrated to nearcomplete dryness with ultra-high-purity nitrogen for use in high-resolution mass spectrometry analysis for structure elucidation and hydrolysis studies.…”

Section: Methodsmentioning

confidence: 99%

The production and hydrolysis of organic nitrates from OH radical oxidation of β-ocimene

et al. 2021

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Abstract. Biogenic volatile organic compounds (BVOCs) emitted by plants represent the largest source of non-methane hydrocarbon emissions on Earth. Photochemical oxidation of BVOCs represents a significant pathway in the production of secondary organic aerosol (SOA), affecting Earth's radiative balance. Organic nitrates (RONO2), formed from the oxidation of BVOCs in the presence of NOx, represent important aerosol precursors and affect the oxidative capacity of the atmosphere, in part by sequestering NOx. In the aerosol phase, RONO2 hydrolyze to form nitric acid and numerous water-soluble products, thus contributing to an increase in aerosol mass. However, only a small number of studies have investigated the production of RONO2 from OH oxidation of terpenes, and among those, few have studied their hydrolysis. Here, we report a laboratory study of OH-initiated oxidation of β-ocimene, an acyclic, tri-olefinic monoterpene released during the daytime from vegetation, including forests, agricultural landscapes, and grasslands. We conducted studies of the OH oxidation of β-ocimene in the presence of NOx using a 5.5 m3 all-Teflon photochemical reaction chamber, during which we quantified the total (gas- and particle-phase) RONO2 yield and the SOA yields. We sampled the organic nitrates produced and measured their hydrolysis rate constants across a range of atmospherically relevant pH. The total organic nitrate yield was determined to be 38(±9) %, consistent with the available literature regarding the dependence of organic nitrate production (from RO2 + NO) on carbon number. We found the hydrolysis rate constants to be highly pH dependent, with a hydrolysis lifetime of 51(±13) min at pH = 4 and 24(±3) min at pH = 2.5, a typical pH for deliquesced aerosols. We also employed high-resolution mass spectrometry for preliminary product identification. The results indicate that the ocimene SOA yield (< 1 %) under relevant aerosol mass loadings in the atmosphere is significantly lower than reported yields from cyclic terpenes, such as α-pinene, likely due to alkoxy radical decomposition and formation of smaller, higher-volatility products. This is also consistent with the observed lower particle-phase organic nitrate yields of β-ocimene – i.e., 1.5(±0.5) % – under dry conditions. We observed the expected hydroxy nitrates by chemical ionization mass spectrometry (CIMS) and some secondary production of the dihydroxy dinitrates, likely produced by oxidation of the first-generation hydroxy nitrates. Lower RONO2 yields were observed under high relative humidity (RH) conditions, indicating the importance of aerosol-phase RONO2 hydrolysis under ambient RH. This study provides insight into the formation and fate of organic nitrates, β-ocimene SOA yields, and NOx cycling in forested environments from daytime monoterpenes not currently included in atmospheric models.

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“…The first fractions eluted with etherpentane solution (206 mg.) showed strong bands at 1730 cm.-1 (17 > C=0)36 and 1623 cm.-1; doublet 1282 and 1271 cm.-1 and 864 cm.-1 (RONO2). 16 This material was heated under reflux for 1 hr. with 8 ml.…”

Section: Methodsmentioning

confidence: 99%

“…Infrared: 1730 cm.-1 (17 > C=0)3« and 1623 cm.-1; doublet 1282 and 1271 cm.-'; 864 cm.-1 (RONO,) 16. …”

mentioning

confidence: 99%

Deamination of the Epimeric 3-Aminoandrost-5-en-17-ones and 6-Amino-3α,5α-cycloandrostan-17-ones

Tadanier¹,

Cole²

1962

J. Org. Chem.

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The infra-red spectra of some organic nitrates

Cited by 26 publications

References 3 publications

Determination of α-pinene-derived organic nitrate yields: particle phase partitioning and hydrolysis

Determination of α-pinene-derived organic nitrate yields: particle phase partitioning and hydrolysis

The production and hydrolysis of organic nitrates from OH radical oxidation of <i>β</i>-ocimene

Deamination of the Epimeric 3-Aminoandrost-5-en-17-ones and 6-Amino-3α,5α-cycloandrostan-17-ones

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The infra-red spectra of some organic nitrates

Cited by 26 publications

References 3 publications

Determination of α-pinene-derived organic nitrate yields: particle phase partitioning and hydrolysis

Determination of α-pinene-derived organic nitrate yields: particle phase partitioning and hydrolysis

The production and hydrolysis of organic nitrates from OH radical oxidation of &lt;i&gt;β&lt;/i&gt;-ocimene

Deamination of the Epimeric 3-Aminoandrost-5-en-17-ones and 6-Amino-3α,5α-cycloandrostan-17-ones

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The production and hydrolysis of organic nitrates from OH radical oxidation of <i>β</i>-ocimene